CN1131846C - Technique for treating sewage by electric dialysis with fast-conductor membrane of biological ions - Google Patents
Technique for treating sewage by electric dialysis with fast-conductor membrane of biological ions Download PDFInfo
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- CN1131846C CN1131846C CN99102691A CN99102691A CN1131846C CN 1131846 C CN1131846 C CN 1131846C CN 99102691 A CN99102691 A CN 99102691A CN 99102691 A CN99102691 A CN 99102691A CN 1131846 C CN1131846 C CN 1131846C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The present invention provides a new technology treating sewage by electric dialysis with a biological-ion fast-conductor membrane, which is a high-energy saving purified sewage-treating electric dialysis device composed of a biological-ion fast-conductor membrane and a membrane electrode with high corrosion resistance and strong electrostatic field. The present invention is characterized in that the surface of the membrane has a good turbulent structure so that large power consumption caused by hydrogen effect, membrane blockage, etc. can be eliminated; the electrode is nonmetal so that the present invention has no falling metal water pollution, and is suitable for black liquor, basic industries, seawater desalination, preparation of purified water, etc.
Description
The protection environment; making full use of water resources is human common heartfelt wishes; scientists go through hardships research, explore to seek the good approach that wastewater comprehensive treatment a kind of both advanced, that efficient is high is recycled, finally think efficient ways, should first-selected ion-exchange membrane electrodialysis method.
Yet, even to this day, because the defective that the manufacture craft of film and material exist, be film in the waste water control application process, because of impurity such as suspended substance in the water are many, film is stopped up, for example black liquid is except the stifled film of impurity such as suspended substance, also have more headache be in the anolyte compartment of silicon with H
+Form the insoluble silicate class in conjunction with the back and be deposited on the film surface.Because the obstruction of film constantly descends the ion exchange capacity of film in time, causes membrane resistance to raise simultaneously.Current efficiency descends, and power consumption increases.Here it is, and traditional new ion-exchange membrane electrodialysis method with occurring modern age can't be applicable to one of reason of waste water control.
In addition, because in electrodialysis process, cathode compartment constantly produces hydrogen, thereby produce a large amount of bubbles, be attached to the film surface and also cause the ion exchange capacity of film to descend, resistance increases, current efficiency descends, and power consumption increases, and this is to adapt to waste water control former therefore two.
The comprehensive ion-exchange membrane electrodialysis device that has occurred at present exists the defective that can not adapt to high-concentration waste water improvement to be summarized as follows in waste water control:
One, it is too high to require influent quality to contain the few requirement of pollution impurity.
Two, pole span is big between anodic-cathodic, and liquid is mobile extreme difference in the slot number chamber, the film vulnerable to pollution.
After three, though the state-of-the-art ion-exchange membrane that occurs at present bubble that hydrogen is produced has film surface irregularity method that the film surface is handled, bubble effect makes moderate progress, but because of the film matte layer is easily stopped up by the contaminated wastewater thing, prolongation in time, this improves effect and loses thereupon.
Four, because anode mostly is the metal galvanic corrosion consumes too greatly, work-ing life is short, and it is electrodialytic 70% that running cost accounts for, and causes the running cost height.
The technology of the present invention is compared with existing domestic and international modern technique and is had following characteristics:
One, the high energy-saving and purifying type waste water control electrodialysis unit that the technology of the present invention is made up of fast electrically conductive film of a kind of biological ion and high special anti-corrosion strong electrostatic field membrane electrode, the film of this device is to utilize a kind of special facture that natural positively charged ion of biomass and the corresponding defective passage of negatively charged ion polymeric material are arranged, this passage is arranged evenly, crooked few, channel spacing compactness is good, non-passage seepage is low, be different from general pure organism film through the crooked fully staggered ionic channel of artificial swelling property, and the ionic channel of the fast electrically conductive film of biological ion of the technology of the present invention almost is a beeline channel, make the ionic travelling speed fast, resistance is little, so film is difficult for contaminated and obstruction.
Two, the fast conductor cationic exchange membrane of biological ion of the present invention, in the polymerization film formation process, because of having imported the fast conductor sulfonation of positively charged ion thalline, decapacitation stops that effectively negatively charged ion passes through film, only allow cation transport to pass through outside the characteristic of film, in making processes, utilize a certain composition of thalline to be dissolved in the characteristic of strong alkali solution, make this be attached to the composition dissolving of the shallow top layer of film during processing, formation is arranged evenly, the extremely shallow network-like structure face of thickness unanimity, when electrodialysis, produce the shallow turbulent flow of table because of galvanic action, make the bubble hydrogen that negative electrode produces can't the coherent film surface, therefore film no hydrogen bubble effect of the present invention, so resistance is less than general electrodialytic membranes, current efficiency is higher than general electrodialytic membranes, its current consumption is the 60-70% of general electrodialytic membranes only, so film ion migration amount is higher than general electrodialytic membranes.
Three, because film of the present invention has special organism to exist, its electrostatic field effect is than the high 20-30% of general electrodialysis unit, so ion migration speed is fast, so be called the fast electrically conductive film of biological ion.Its pole span is zero pole span (or minimum pole span 0.3mm-1.0mm), and generally be used for the 18cm-20cm that is of electrodialysis pole span minimum that high-concentration waste water handles, and fast its pole span of electrically conductive film electrodialysis unit of biological ion of the present invention is zero, utmost point chamber liquid Turbulence Flow is good, so pollutent is difficult for the stifled film of deposition.
Four, the biological ion of the present invention special-purpose anode of fast conductor electrodialysis (or negative electrode) is a kind of conducting film that special strong electrostatic field thalline is made non-metallic body that imported, and does not therefore have the galvanic corrosion consumption of electrode.
Because of electrode belongs to nonmetal character, there is not metallicity galvanic corrosion thing to refute, also heavy metal free utmost point water generates from the environment protection angle, is to belong to the advanced electrodialysis unit of a kind of high cleaning, energy-saving type waste water control.
The advanced advantage of comprehensive the technology of the present invention is:
One, high resistance to crocking, high purification property.
Two, energy-efficient property and high chemical stability.
Three, wide adaptability can be used for the preparation of high density waste water treatment comprehensive reutilizations such as black liquid, high sulfate radical, high salt, chlorine industry (or sodium sulfate alkali-making process), sea water desaltination, pure water etc.Main purpose of the present invention realizes by following technology: the manufacturing technology of a kind of biological quick ion conductor film electrodialytic method one, the fast electrically conductive film of biological ion.(1) manufacturing technology of the fast electrically conductive film anode membrane of biological ion.
1, film strengthens body: the terylene screen cloth
2, main body material name title and weight part:
60 parts in special sulfonation bacterium fast-ionic conductor powder (600 order);
15 parts of vinylbenzene; 15 parts of tetrafluoroethylene;
6 parts of Vinylstyrenes; 2 parts of ethylene methacrylic ketone;
0.5 part of Diisopropyl azodicarboxylate; 1.5 parts of doping agents.
3, auxiliary material title and weight part:
30 parts of sulphonating agents; 70 parts of chlorizating agents;
Aqueous sulfuric acid is an amount of.
4, technology:
(1) in the reactor that has condenser and agitator, press proportional quantity and add sulfonation bacterium fast-ionic conductor powder, vinylbenzene, Vinylstyrene, ethylene methacrylic ketone and Diisopropyl azodicarboxylate slowly are heated to 60 ℃ under constantly stirring, reacted 1 hour, and generated thick material.
(2) will cool off the thickness reactant that bubble is removed in the back, slowly be poured on the film forming template, then two templates be stacked smoothly, make the thick film of 0.2mm that is, again in 60 ℃ of left and right sides heated polymerizables 4 hours.
(3) remove the film forming template, heated 2-3 hour down at 60-70 ℃ again, promptly make water white soft basement membrane.
(4) under dry moistureproof condition, the basement membrane that makes is placed on filled in chlorizating agent and the sulphonating agent mixing solutions dipping 20 hours, wash with the aqueous sulfuric acid of different concns successively again, make the chlorine sulfo group be converted into sulfonic group.Wash with water at last.
(5) with carboxylic acyl group solution and the one side of coating film after fast-ionic conductor bacterium powder mixes; make sulfonic group transfer the carboxyl acyl chloride base to; flood with propyl carbinol again; be blown into air simultaneously, and heat and carry out chloridized, make the carboxyl acyl chloride base transfer the carboxylic acid group to; film after treatment is the existing sulfonic group of the fast electrically conductive film of biological ion; carboxylic acid bonded film is arranged again, again after abundant washing, in drying at room temperature to constant weight.
(6) be the flat network thalline mixture water furnishing pasty state of 5um with average grain, this mashed prod is coated on the filter paper, after the drying, form flat network thalline layer on the paper surface.Then above-mentioned film two sides is coated with flat network thalline metafiltration paper and heats (160 ℃ with this, 2.94MPa) condition under pressurize, the reseal membrane goods are immersed in the basic solution, make be dissolved in alkaline components dissolving in the thalline after, form network-like structure on the film surface, in methyl alcohol, soaked (60 ℃) 5 hours again, take out in 25 ℃ of air dryings 48 hours, the lattice chain line face of the uniformity that its surface of film after treatment forms, can be when electrodialysis in electrolyte solution, can form good turbulence effect, the bubble that elimination produces because of hydrogen causes membrane resistance to increase, and bath voltage rises.And can prevent the obstruction of film, thus greatly improved current efficiency, reduced power consumption.(2) making of the fast conductor cavity block of biological ion.
1, film strengthens body; The terylene screen cloth
2, main body material title and weight part:
60 parts in special amination bacterium fast-ionic conductor powder (600 order);
15 parts of vinylbenzene; 15 parts of tetrafluoroethylene;
6 parts of Vinylstyrenes; 2 parts of ethylene methacrylic ketone;
0.5 part of Diisopropyl azodicarboxylate; 1.5 parts of doping agents.
3, auxiliary material title and weight part:
N-methyl croak piperazine is an amount of; Methyl alcohol is an amount of;
Lithium chloride is an amount of; 10%NaOH-CH
3The OH mixing solutions is an amount of.
4, technology
(1) the main body material is mixed the back and be made into basement membrane with the method for making anode membrane.
(2) with film 10%NaOH-CH
3The OH mixed aqueous solution carries out saponification (hydrolysis), again 50 ℃ with N-methyl croak piperazine methyl alcohol mixed liquor in hot 48h altogether, in methyl alcohol and lithium chloride solution, react 24h again, must contain the fast conductor anion-exchange membrane of quaternary ammonium salt biological ion.(3) high special anti-corrosion strong electrostatic field membrane electrode manufacturing technology
This high special anti-corrosion strong electrostatic field membrane electrode, main as the electrodialysis anode, belong to non-metal type, there is not galvanic corrosion (or minimum) in the electrodialysis working process, the electric conductivity height has high special solidity to corrosion again, and no galvanic corrosion metal refuting property utmost point water pollutes, and stronger electrostatic effect is arranged, have high purification, high energy-saving effect.
1, electrode materials is formed:
(1) material of main part and weight part:
60 parts of sulfonation fluoric acid mixed Ni leach liquors; 10 parts of butanone;
10 parts of lithium fluoride; 15 parts of ethylene glycol monomethyl ethers;
Iodine (I
2) 2 parts; Resins, epoxy is an amount of.
(2) manufacture craft:
1. nickel leach liquor, butanone, lithium fluoride, di-alcohol monomethyl ether are mixed into ionogen.
2. make anode with sheet glass, make negative electrode with nickel.
3. on anode, be coated with Resins, epoxy, after waiting to solidify, carry out the electrolytic polymerization film forming.Operational condition is at 2mA/cm
2The condition of current density under oxidation 60min, promptly on anode, form the uniform conductive film, thickness is 16 Ц m; Carry out pore with pore-creating agent as required again.Two, installation and the using method of the fast electrically conductive film of biological ion in electrodialyzer:
1, reclaiming NaOH with black liquid alkali (NaOH) recovery and other trade effluent is the example explanation:
(1) installation of film and electrode
1. with the frame of plastic support of film and electrode, with～thick the space of 40mm frame of plastic as entering sewage utmost point chamber (anolyte compartment), it is anode that the strong electrostatic field membrane electrode of high special solidity to corrosion is loaded onto in both sides, biological quick ion conductor film (anode membrane) is contained in by forming the anolyte compartment on the inboard frame of plastic of electrode, is close between film and the electrode.
2. reclaim the NaOH cathode compartment with the～thick space of 40mm frame of plastic as advancing tap water, biological quick ion conductor film (anode membrane) is close to frame of plastic, and the dress stainless steel cathode is close on the film surface, and anode is 1.0mm with the negative electrode distance; According to black liquor treatment capacity difference, and make and corresponding electrodialyzer, alternately arrange the cathode and anode chamber during assembling, and anolyte compartment and cathode compartment separate with anode membrane, connect with channel-section steel between the strip electrode chamber, and screw is fastened to non-leakage being as the criterion; Current density is 30-40A/bm during work
2Monofilm, voltage 3.0-3.25V.All can for temperature 5-90 ℃.About power consumption 1200KW/NaOHHt.
2, be recycled as example with high concentration sulphate and high ammonia-nitrogen wastewater, what be different from black liquid is:
The fast conductor cavity block of biological ion is all loaded onto in anode frame of plastic two sides, the fast conductor anode membrane of biological ion is all loaded onto in negative electrode frame of plastic two sides, electrode and film are close to, link to each other with a conductor between cathode compartment (frame) and anolyte compartment's (frame) electrode, pole span is 0.6-1.0mm, the reclaim(ed) sulfuric acid root SO of assembling mode anolyte compartment
4 2-, cathode compartment reclaims NH
4 +(ammonia), middle boxes chamber are waste water chamber (advancing waste water), the two poles of the earth interventricular septum 40mm, and current density is 30-40A/bm during work
2, voltage 3.0-3.25V all can for temperature 5-90 ℃.
Claims (1)
1, the fast electrically conductive film electrodialytic method of a kind of biological ion is characterized in that: the making of the fast electrically conductive film anode membrane of making biological ion of the fast electrically conductive film of biological ion: film strengthens body: terylene screen cloth main body material title and weight part:
60 parts in special sulfonation bacterium fast-ionic conductor powder 600 orders;
15 parts of vinylbenzene; 15 parts of tetrafluoroethylene;
6 parts of Vinylstyrenes; 2 parts of ethylene methacrylic ketone;
0.5 part of Diisopropyl azodicarboxylate; 1.5 parts of doping agents; Auxiliary material title and weight part:
30 parts of sulphonating agents; 70 parts of chlorizating agents;
Aqueous sulfuric acid is an amount of; Technology:
In the reactor that has condenser and agitator, press proportional quantity and add sulfonation bacterium fast-ionic conductor powder, vinylbenzene, Vinylstyrene, ethylene methacrylic ketone and Diisopropyl azodicarboxylate slowly are heated to 60 ℃ under constantly stirring, reacted 1 hour, and generated thick material;
The thickness reactant of bubble is removed in cooling back, slowly be poured on the film forming template, then two templates are stacked smoothly, make the thick film of 0.2mm that is, again in 60 ℃ of following heated polymerizables 4 hours;
Remove the film forming template, heated 2-3 hour down at 60-70 ℃ again, promptly make water white soft basement membrane;
Under dry moistureproof condition, the basement membrane that makes is placed on filled in chlorizating agent and the sulphonating agent mixing solutions dipping 20 hours, wash with the aqueous sulfuric acid of different concns successively again, make the chlorine sulfo group be converted into sulfonic group, wash with water at last;
With carboxylic acyl group solution and the one side of coating film after fast-ionic conductor thalline powder mixes, make sulfonic group transfer the carboxyl acyl chloride base to, flood with propyl carbinol again, be blown into air simultaneously, and heat and carry out chloridized, make the carboxyl acyl chloride base transfer the carboxylic acid group to, film after treatment is the existing sulfonic group of the fast electrically conductive film of biological ion, carboxylic acid group's bonded film is arranged again, again after abundant washing, in drying at room temperature to constant weight;
With average grain is the flat network thalline mixture water furnishing pasty state of 5um, this mashed prod is coated on the filter paper, after the drying, form flat network thalline layer on the paper surface, then above-mentioned film two sides is coated with flat network thalline metafiltration paper and heats with this, at 160 ℃, 2.94MPa condition under pressurize, the reseal membrane goods are immersed in the basic solution, make be dissolved in alkaline components dissolving in the thalline after, form network-like structure on the film surface, in methyl alcohol, soak again 60 ℃ 5 hours, take out in 25 ℃ of air dryings 48 hours the lattice chain line face of the uniformity that its surface of film after treatment forms; The making of the fast conductor cavity block of biological ion: film strengthens body; Terylene screen cloth main body material title and weight part:
60 parts in special amination bacterium fast-ionic conductor powder 600 orders;
15 parts of vinylbenzene; 15 parts of tetrafluoroethylene;
6 parts of Vinylstyrenes; 2 parts of ethylene methacrylic ketone;
0.5 part of Diisopropyl azodicarboxylate; 1.5 parts of doping agents; Auxiliary material title and weight part:
N-methyl croak piperazine is an amount of; Methyl alcohol is an amount of;
Lithium chloride is an amount of; The 10%NaOH-CH3OH mixing solutions is an amount of; Technology
The main body material is mixed the back be made into basement membrane with the method for making anode membrane;
With film 10%NaOH-CH
3The OH mixed aqueous solution carries out the saponification hydrolysis, again 50 ℃ with N-methyl croak piperazine methyl alcohol mixed liquor in hot 48h altogether, in methyl alcohol and lithium chloride solution, react 24h again, must contain the fast conductor anion-exchange membrane of quaternary ammonium salt biological ion; High special anti-corrosion strong electrostatic field membrane electrode manufacturing technology
Electrode materials is formed: material of main part and weight part:
60 parts of sulfonation fluoric acid mixed Ni leach liquors; 10 parts of butanone;
10 parts of lithium fluoride; 15 parts of ethylene glycol monomethyl ethers;
Iodine (I
2) 2 parts; Resins, epoxy is an amount of; Manufacture craft:
Nickel leach liquor, butanone, lithium fluoride, di-alcohol monomethyl ether are mixed into ionogen;
Make anode with sheet glass, make negative electrode with nickel;
On anode, be coated with Resins, epoxy, after waiting to solidify, carry out the electrolytic polymerization film forming; Operational condition is at 2mA/cm
2The condition of current density under oxidation 60min, promptly on anode, form the uniform conductive film, thickness is 16um; Carry out pore with pore-creating agent as required again; Installation and the using method of the fast electrically conductive film of biological ion in electrodialysis
Reclaim the installation that NaOH illustrates film and electrode with black liquid alkali (NaOH) recovery and other trade effluent:
With the frame of plastic is the support of film and electrode, with the thick space of 40mm frame of plastic as entering anolyte compartment, sewage utmost point chamber, it is anode that the strong electrostatic field membrane electrode of high special solidity to corrosion is loaded onto in both sides, and biological quick ion conductor film anode membrane is contained in by forming the anolyte compartment on the inboard frame of plastic of electrode, is close between film and the electrode;
Reclaim the NaOH cathode compartment with the thick space of 40mm frame of plastic as advancing tap water, biological quick ion conductor film anode membrane is close to frame of plastic, and the dress stainless steel cathode is close on the film surface, and anode and negative electrode distance are 1.0mm; According to black liquor treatment capacity difference, and make and corresponding electrodialyzer, alternately arrange the cathode and anode chamber during assembling, and anolyte compartment and cathode compartment separate with anode membrane, connect with channel-section steel between the strip electrode chamber, and screw is fastened to non-leakage being as the criterion; Current density is 40A/bm during work
2Monofilm, voltage 3.0V;
With what high concentration sulphate and high ammonia-nitrogen wastewater recycling were different from black liquid be:
The fast conductor cavity block of biological ion is all loaded onto in anode frame of plastic two sides, the fast conductor anode membrane of biological ion is all loaded onto in negative electrode frame of plastic two sides, and electrode and film are close to, and links to each other with a conductor between cathode chamber frame and anolyte compartment's frame electrode, pole span is 1.0mm, the reclaim(ed) sulfuric acid root SO of assembling mode anolyte compartment
4 2-, cathode compartment reclaims NH
4 +, waste water is advanced for the waste water chamber in the middle boxes chamber, the two poles of the earth interventricular septum 40mm, and current density is 40A/bm during work
2, voltage 3.0V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99102691A CN1131846C (en) | 1999-04-17 | 1999-04-17 | Technique for treating sewage by electric dialysis with fast-conductor membrane of biological ions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99102691A CN1131846C (en) | 1999-04-17 | 1999-04-17 | Technique for treating sewage by electric dialysis with fast-conductor membrane of biological ions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1245148A CN1245148A (en) | 2000-02-23 |
| CN1131846C true CN1131846C (en) | 2003-12-24 |
Family
ID=5270935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99102691A Expired - Fee Related CN1131846C (en) | 1999-04-17 | 1999-04-17 | Technique for treating sewage by electric dialysis with fast-conductor membrane of biological ions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1131846C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527236B (en) * | 2011-11-30 | 2014-04-02 | 许裕金 | Preparation method for seawater desalting device with fast ion conductor embedded film |
| CN102531180B (en) * | 2011-12-05 | 2013-10-09 | 北京市水利科学研究所 | Application of fast ion conductor as alga suppression material |
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1999
- 1999-04-17 CN CN99102691A patent/CN1131846C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1245148A (en) | 2000-02-23 |
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